JP3961604B2 - Method for producing composite silica fine particles - Google Patents

Description

【００５９】
ＡＩＢＮ：２，２’−アゾビスイソブチロニトリル
ＡＤＶＮ：２，２’−アゾビス（２，４−ジメチルバレロニトリル）
ＭＭＡ：メチルメタクリレート
２−ＥＨＡ：２−エチルヘキシルアクリレート
Ｓｔ：スチレン
ＨＥＡ：２−ヒドロキシエチルアクリレート
ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
ＰＯＥＭＡ：ポリオキシメチレンメタクリレート
ＡＡ：アクリル酸
Ｓ−１：重合性ポリシロキサン（Ｓ−１）
（製造例６）
（球状シリカ微粒子分散溶媒（Ｄ−１）の製造）
攪拌機、２つの滴下口（滴下口イおよび滴下口ロ）、温度計を備えた１リットルの四つ口フラスコに、酢酸ブチル５１１ｇ、メタノール１２８ｇを入れておき、内温を２０℃に調整した。ついでフラスコ内を攪拌しながら、テトラメトキシシラン１０８ｇを滴下口イから、水４１ｇ、２５％アンモニア水１４ｇ、メタノール５５ｇの混合液を滴下口ロから、４０分かけて滴下した。滴下後、同温度で１時間攪拌を続け、球状シリカ微粒子分散溶媒（Ｄ−１）を得た。得られた球状シリカ微粒子の平均粒子径、変動係数および球状シリカ微粒子分散溶媒（Ｄ−１）の液組成を表２に示す。
【００６０】
なお、球状シリカ微粒子および後述の複合シリカ微粒子の平均粒子径、変動係数は以下の方法で測定した。
（平均粒子径および変動係数）
透過型電子顕微鏡により粒子を撮影し、任意の１００個の粒子の直径を読み取り、その平均を平均粒子径とした。また、下記の式により変動係数を算出した。
【００６１】
変動係数（％）＝（粒子の粒子径の標準偏差）／（粒子の平均粒子径）
（製造例７）
（球状シリカ微粒子分散溶媒（Ｄ−２）の製造）
攪拌機および超音波ホモジナイザーを備えた１リットルのマイヤーフラスコに、メタノール６９６ｇ、（株）日本触媒製球状シリカ微粒子粉体「シーホスターＫＥ−Ｐ１００」２４ｇを入れ、１時間超音波分散を行った。次いでアンモニア水８０ｇを加え、室温にて１時間攪拌を行い、球状シリカ微粒子分散溶媒（Ｄ−２）を得た。得られた溶媒中の球状シリカ微粒子の平均粒子径、変動係数および球状シリカ微粒子分散溶媒（Ｄ−２）の液組成を表２に示す。
（製造例８）
（球状シリカ微粒子分散溶媒（Ｄ−３）の製造）
球状シリカ微粒子粉体として（株）日本触媒製「シーホスター ＫＥ−Ｐ２５０」を用いること以外は製造例７と同様にして、球状シリカ微粒子分散溶媒（Ｄ−３）を得た。得られた溶媒中の球状シリカ微粒子の平均粒子径、変動係数および球状シリカ微粒子分散溶媒（Ｄ−３）の液組成を表２に示す。
（製造例９）
（球状シリカ微粒子分散溶媒（Ｄ−４）の製造）
攪拌機、２つの滴下口（滴下口イおよび滴下口ロ）、温度計を備えた５００ミリリットルの四つ口フラスコに、メタノール２２９ｇ、２５％アンモニア水３６ｇを入れておき、内温を２０℃に調整した。ついでフラスコ内を攪拌しながら、テトラメトキシシラン７３ｇを滴下口イから、水１７ｇを滴下口ロから、４０分かけて滴下した。滴下後、同温度で１時間攪拌を続け、球状シリカ微粒子分散溶媒（Ｄ−４）を得た。得られた球状シリカ微粒子の平均粒子径、変動係数および球状シリカ微粒子分散溶媒（Ｄ−４）の液組成を表２に示す。
（製造例１０）
（球状シリカ微粒子分散溶媒（Ｄ−５）の製造）
攪拌機を備えた１リットルのマイヤーフラスコに、メタノール６８８ｇ、日産化学工業（株）製「スノーテックスＣ」４０ｇ、アンモニア水７２ｇを入れ、１時間攪拌を行い、球状シリカ微粒子分散溶媒（Ｄ−５）を得た。得られた溶媒中の球状シリカ微粒子の平均粒子径、変動係数および球状シリカ微粒子分散溶媒（Ｄ−５）の液組成を表２に示す。
【００６２】
【表２】

【００６３】
（実施例Ａ１）
（複合シリカ微粒子（Ｚ−１）分散体の製造）
攪拌機、滴下口、温度計を備えた５００ミリリットルの四つ口フラスコに、製造例６で得た球状シリカ微粒子分散溶媒（Ｄ−１）３５０ｇを入れておき、内温を２０℃に調整した。ついでフラスコ内を攪拌しながら、製造例２で得た有機ポリマー（Ｐ−１）の酢酸ブチル溶液４．５ｇ、酢酸ブチル４．５ｇの混合液を２０分かけて滴下した。滴下後、同温度で１時間攪拌を続けた。さらに１１０ｍｍＨｇの圧力下、フラスコ内温を１００℃まで昇温し、アンモニア、メタノール、水、酢酸ブチルを固形分が２５％となるまで留去し、複合シリカ微粒子（Ｚ−１）の酢酸ブチル分散体を得た。得られた複合シリカ微粒子（Ｚ−１）の平均粒子径、変動係数、この微粒子中のシリカ濃度を表３に示す。
【００６４】
なお、複合シリカ微粒子の平均粒子径および変動係数は、前述の方法で測定した。また、複合シリカ微粒子中のシリカ濃度は以下の方法で測定した。
（複合シリカ微粒子中のシリカ濃度）
複合シリカ微粒子分散体を乾燥して得られる複合シリカ微粒子粉体について元素分析を行い、灰分をシリカとして算出した。
（実施例Ａ２）
（複合シリカ微粒子（Ｚ−２）分散体の製造）
攪拌機、滴下口、温度計を備えた５００ミリリットルの四つ口フラスコに、製造例７で得た球状シリカ微粒子分散溶媒（Ｄ−２）３８０ｇを入れておき、内温を２０℃に調整した。ついでフラスコ内を攪拌しながら、製造例３で得た有機ポリマー（Ｐ−２）のメタノール溶液４ｇ、メタノール４ｇの混合液を２０分かけて滴下した。滴下後、同温度で１時間攪拌を続けた。さらに６０ｍｍＨｇの圧力下、フラスコ内温を１２５℃まで昇温し、アンモニア、メタノール、水を留去しながらエチレングリコール１０３ｇを滴下し、固形分が１０％となるまで濃縮し、複合シリカ微粒子（Ｚ−２）のエチレングリコール分散体を得た。得られた複合シリカ微粒子（Ｚ−２）の平均粒子径、変動係数、この微粒子中のシリカ濃度を表３に示す。
（実施例Ａ３）
（複合シリカ微粒子（Ｚ−３）分散体の製造）
攪拌機、滴下口、温度計を備えた５００ミリリットルの四つ口フラスコに、製造例８で得た球状シリカ微粒子分散溶媒（Ｄ−３）３８０ｇを入れておき、内温を２０℃に調整した。ついでフラスコ内を攪拌しながら、製造例４で得た有機ポリマー（Ｐ−３）のメタノール溶液９．２ｇ、メタノール９．２ｇの混合液を２０分かけて滴下した。滴下後、同温度で１時間攪拌を続けた。さらに６０ｍｍＨｇの圧力下、フラスコ内温を１２５℃まで昇温し、アンモニア、メタノール、水を留去しながらエチレングリコール１０３ｇを滴下し、固形分が１０％となるまで濃縮し、複合シリカ微粒子（Ｚ−３）のエチレングリコール分散体を得た。得られた複合シリカ微粒子（Ｚ−３）の平均粒子径、変動係数、この微粒子中のシリカ濃度を表３に示す。
（実施例Ａ４）
（複合シリカ微粒子（Ｚ−４）分散体の製造）
攪拌機、滴下口、温度計を備えた５００ミリリットルの四つ口フラスコに、製造例９で得た球状シリカ微粒子分散溶媒（Ｄ−４）３５０ｇを入れておき、内温を２０℃に調整した。ついでフラスコ内を攪拌しながら、製造例５で得た有機ポリマー（Ｐ−４）のメタノール溶液１６ｇ、メタノール１６ｇの混合液を２０分かけて滴下した。滴下後、同温度で１時間攪拌を続けた。さらに６０ｍｍＨｇの圧力下、フラスコ内温を１２５℃まで昇温し、アンモニア、メタノール、水を留去しながらエチレングリコール２５７ｇを滴下し、固形分が１０％となるまで濃縮し、複合シリカ微粒子（Ｚ−４）のエチレングリコール分散体を得た。得られた複合シリカ微粒子（Ｚ−４）の平均粒子径、変動係数、この微粒子中のシリカ濃度を表３に示す。
（実施例Ａ５）
（複合シリカ微粒子（Ｚ−５）分散体の製造）
攪拌機、滴下口、温度計を備えた５００ミリリットルの四つ口フラスコに、製造例１０で得た球状シリカ微粒子分散溶媒（Ｄ−５）３８０ｇを入れておき、内温を２０℃に調整した。ついでフラスコ内を攪拌しながら、製造例３で得た有機ポリマー（Ｐ−２）のメタノール溶液１．５ｇ、メタノール６．５ｇの混合液を２０分かけて滴下した。滴下後、同温度で１時間攪拌を続けた。さらに６０ｍｍＨｇの圧力下、フラスコ内温を１２５℃まで昇温し、アンモニア、メタノール、水を留去しながらエチレングリコール３４ｇを滴下し、固形分が１０％となるまで濃縮し、複合シリカ微粒子（Ｚ−５）のエチレングリコール分散体を得た。得られた複合シリカ微粒子（Ｚ−４）の平均粒子径、変動係数、この微粒子中のシリカ濃度を表３に示す。
（実施例Ａ６）
（複合シリカ微粒子（Ｚ−６）の製造）
攪拌機、滴下口、温度計を備えた５００ミリリットルの四つ口フラスコに、製造例７で得た球状シリカ微粒子分散溶媒（Ｄ−２）３３０ｇを入れておき、内温を２０℃に調整した。ついでフラスコ内を攪拌しながら、製造例３で得た有機ポリマー（Ｐ−２）のメタノール溶液３０ｇ、メタノール３０ｇの混合液を４０分かけて滴下した。滴下後、同温度で１時間攪拌を続けた。さらに常圧下、フラスコ内温を７０℃まで昇温し、アンモニア、メタノール、水を留去し、固形分が３０％となるまで濃縮した。さらに減圧乾燥器内で５０ｍｍＨｇの圧力下、１２０℃で２時間保持し、複合シリカ微粒子（Ｚ−６）の乾燥体を得た。得られた複合シリカ微粒子（Ｚ−６）の平均粒子径、変動係数、この微粒子中のシリカ濃度を表３に示す。
【００６５】
【表３】

【００６６】
（比較例Ａ１）
（球状シリカ微粒子の表面処理）
攪拌機、滴下口、温度計を備えた５００ミリリットルの四つ口フラスコに、製造例７で得た球状シリカ微粒子分散溶媒（Ｄ−２）３８０ｇを入れておき、内温を２０℃に調整した。ついでフラスコ内を攪拌しながら、メチルトリメトキシシラン４ｇ、メタノール４ｇの混合液を３０分かけて滴下した。滴下後、同温度で１時間攪拌を続けた。得られた液中には、製造例７で得た球状シリカ微粒子以外に新たに微小粒子が生成しており、球状シリカ微粒子の表面処理はうまく行えなかった。
（比較例Ａ２）
（球状シリカ微粒子の表面処理）
攪拌機および超音波ホモジナイザーを備えた１リットルのマイヤーフラスコに、メタノール６９６ｇ、（株）日本触媒製球状シリカ微粒子粉体「シーホスターＫＥ−Ｐ１００」２４ｇを入れ、１時間超音波分散を行った。次いでメチルトリメトキシシラン０．２ｇを加え、室温にて１時間攪拌を行った。減圧乾燥器内で５０ｍｍＨｇの圧力下、１２０℃で２４時間加熱乾燥し、球状シリカ微粒子の表面処理品粉体（Ｚ’−１）を得た。
（比較例Ａ３）
（球状シリカ微粒子分散体の製造）
攪拌機および超音波ホモジナイザーを備えた３００ミリリットルのマイヤーフラスコに、（株）日本触媒製球状シリカ微粒子粉体「シーホスター ＫＥ−Ｐ１００」２０ｇ、エチレングリコール１８０ｇを入れ、１時間超音波分散を行った。次いで室温にて１時間攪拌を行い、球状シリカ微粒子エチレングリコール分散体を得た。
（比較例Ａ４）
（球状シリカ微粒子分散体の製造）
比較例Ａ２で得た球状シリカ微粒子の表面処理品粉体（Ｚ’−１）を用いること以外は比較例Ａ１と同様にして、球状シリカ微粒子エチレングリコール分散体を得た。
（実施例Ｂ１）
（プラスチックフィルム（Ｆ−１）の製造）
製造例１で得られた複合シリカ微粒子の酢酸ブチル分散体（Ｚ−１）１ｇ、（株）日本触媒製ポリエステル樹脂「アロプラッツＢＯ−１１０」１５ｇ、酢酸ブチル４００ｇを混合して塗布液とした。この塗布液を、ポリエチレンテレフタレートフィルムの片面にバーコーターで塗布し、室温で２０分、１４０℃で２０分乾燥した。得られたプラスチックフィルム（Ｆ−１）の滑り性（動摩擦係数）および耐摩耗性、プラスチックフィルム中の複合シリカ微粒子とフィルムを構成する樹脂との親和性についての試験結果を表４に示す。得られたプラスチックフィルムの滑り性、耐摩耗性および親和性は良好であった。
【００６７】
なお、プラスチックフィルムの評価は以下の方法で行った。
（動摩擦係数）
フィルムを２００×１００ｍｍに切り、下記の装置で測定した。
ＨＥＩＤＯＮ製 連続荷重式表面性測定機 ＴＹＰＥ：ＨＥＩＤＯＮ−２２（耐摩耗性）
長さ４０ｃｍ、幅１５ｍｍのフィルムの両端に２０ｇの荷重をかけて、折り曲げ角１５０度で直径５ｍｍのステンレス製ピンを２００回往復して摩擦させた。
【００６８】
外観でスクラッチの有無を観察し、スクラッチのほとんど無いものを○、スクラッチの多いものを×、その中程度のものを△とした。
（親和性）
上記耐摩耗性を調べた後、フィルムの表面を走査型電子顕微鏡により観察し、粒子の脱落のほとんど無いものを○、粒子の脱落の多いものを×、その中程度のものを△とした。
（実施例Ｂ２）
（プラスチックフィルム（Ｆ−２）の製造）
製造例１で得られた複合シリカ微粒子の酢酸ブチル分散体（Ｚ−１）１ｇ、（株）日本触媒製アクリル樹脂「アロタン２０６０」１５ｇ、住友化学工業（株）製イソシアネート硬化剤「スミジュールＮ−３５００」２．５ｇ、酢酸ブチル４００ｇを混合して塗布液とした。この塗布液を、ポリエチレンテレフタレートフィルムの片面にバーコーターで塗布し、室温で３０分、８０℃で４０分乾燥した。得られたプラスチックフィルム（Ｆ−２）の滑り性（動摩擦係数）、耐摩耗性および親和性についての試験結果を表４に示す。
（実施例Ｂ３）
（プラスチックフィルム（Ｆ−３）の製造）
製造例１で得られた複合シリカ微粒子の酢酸ブチル分散体（Ｚ−１）１ｇ、（株）日本触媒製アクリル樹脂「ユーダブルＳ−５１４０ＳＰＬ」１５ｇ、酢酸ブチル４００ｇを混合して塗布液とした。この塗布液を、ポリエチレンフィルムの片面にバーコーターで塗布し、室温で２０分、６０℃で４０分乾燥した。得られたプラスチックフィルム（Ｆ−３）の滑り性（動摩擦係数）、耐摩耗性および親和性についての試験結果を表４に示す。
（比較例Ｂ１）
（プラスチックフィルム（Ｆ’−１）の製造）
（株）日本触媒製球状シリカ微粒子粉体「シーホスター ＫＥ−Ｐ１００」０．５ｇ、（株）日本触媒製ポリエステル樹脂「アロプラッツＢＯ−１１０」３０ｇ、酢酸ブチル８００ｇを混合後、３０分超音波分散して塗布液とした。この塗布液を、ポリエチレンテレフタレートフィルムの片面にバーコーターで塗布し、室温で２０分、１４０℃で２０分乾燥した。得られたプラスチックフィルム（Ｆ’−１）の滑り性（動摩擦係数）、耐摩耗性および親和性についての試験結果を表４に示す。
（比較例Ｂ２）
（プラスチックフィルム（Ｆ’−２）の製造）
球状シリカ微粒子として比較例Ａ２で得た球状シリカ微粒子の表面処理品粉体（Ｚ’−１）０．５ｇを用いること以外は比較例Ｂ１と同様にしてプラスチックフィルム（Ｆ’−２）を得た。得られたプラスチックフィルム（Ｆ’−２）の滑り性（動摩擦係数）、耐摩耗性および親和性についての試験結果を表４に示す。
（実施例Ｂ４）
（プラスチックフィルム（Ｆ−４）の製造）
撹拌機、温度計、冷却管および流出口が接続した蒸留塔を備えた５００ミリリットルの四つ口フラスコに、ジメチルテレフタレート１００ｇおよびエチレングリコール７０ｇに触媒として酢酸マンガン四水和物０．０４ｇを加え、２３０℃まで昇温してメタノールを留去してエステル交換反応を行った。次いで実施例Ａ２で得られた複合シリカ微粒子（Ｚ−２）のエチレングリコール分散体３ｇおよび三酸化アンチモン０．０３ｇを攪拌しながら添加した後、１ｍｍＨｇの圧力下、２８０℃まで昇温して重縮合を行い、ポリエステル樹脂を得た。このポリエステル樹脂を、２９０℃に設定した押出機でシート状に押出し、次いで９０℃で縦方向に３．５倍に延伸後、１００℃で横方向に４倍延伸し、２１０℃で１０秒間熱処理を行って、プラスチックフィルム（Ｆ−４）を得た。得られたプラスチックフィルムの滑り性および耐摩耗性は良好であった。得られたプラスチックフィルム（Ｆ−４）の滑り性（動摩擦係数）、耐摩耗性および親和性についての試験結果を表４に示す。
（実施例Ｂ５〜Ｂ７）
（プラスチックフィルム（Ｆ−５〜Ｆ−７）の製造）
表４に示した複合シリカ微粒子のエチレングリコール分散体を用いること以外は実施例Ｂ４と同様にして、プラスチックフィルム（Ｆ−５〜Ｆ−７）を得た。得られたプラスチックフィルム（Ｆ−５〜Ｆ−７）の滑り性（動摩擦係数）、耐摩耗性および親和性についての試験結果を表４に示す。
（比較例Ｂ３〜Ｂ４）
（プラスチックフィルム（Ｆ’−３〜Ｆ’−４）の製造）
比較例Ａ３および比較例Ａ４で得た球状シリカ微粒子エチレングリコール分散体を用いること以外は実施例Ｂ４と同様にして、プラスチックフィルム（Ｆ’−３〜Ｆ’−４）を得た。得られたプラスチックフィルム（Ｆ’−３〜Ｆ’−４）の滑り性（動摩擦係数）、耐摩耗性および親和性についての試験結果を表４に示す。
（実施例Ｂ８）
（プラスチックフィルム（Ｆ−８）の製造）
ポリプロピレン（メルトフローインデックス（ＭＩ）２ｇ／１０分，ヘプタン可溶分３％）９７部に対して、実施例Ａ６で得られた複合シリカ微粒子（Ｚ−６）の乾燥体を３部配合して、バンバリーミキサーにて２３０℃で練り込み、ペレットを得た。次いで、このペレット１０部と、上記ポリプロピレン９０部とを混合し、２６０℃に設定した押出機でシート状に押出し、次いで１７５℃で縦方向に５倍に延伸後、同温度で横方向に９倍延伸し、プラスチックフィルム（Ｆ−８）を得た。得られたプラスチックフィルム（Ｆ−８）の滑り性（動摩擦係数）、耐摩耗性および親和性についての試験結果を表４に示す。
（実施例Ｂ９）
（プラスチックフィルム（Ｆ−９）の製造）
低密度ポリエチレン（メルトフローインデックス（ＭＩ）２ｇ／１０分，密度０．９２ｇ／ｃｍ ^３ ）９５部に対して、実施例６で得られた複合シリカ微粒子（Ｚ−６）の乾燥体を５部配合して、バンバリーミキサーにて２２０℃で練り込み、ペレットを得た。次いで、このペレット８部と、上記ポリエチレン９２部とを混合し、２００℃に設定した押出機でシート状にＴダイより押出し、プラスチックフィルム（Ｆ−９）を得た。得られたプラスチックフィルム（Ｆ−９）の滑り性（動摩擦係数）、耐摩耗性および親和性についての試験結果を表４に示す。
【００６９】
【表４】

【００７０】
（実施例Ｃ１）
平均粒子径０．３μｍの塩化銀結晶を０．０５Ｎヨウ化カリウム溶液で処理し、得られた沈殿を精製した。再溶解後、塩化金酸で処理したものと、４−ヒドロキシ−６−メチル−１，３，３ａ−７−テトラザイデンと、界面活性剤と、硬膜剤とを混合して、乳剤を調製した。この乳剤を、ポリエチレンテレフタレートフィルム（ＰＥＴフィルム）上にコートして、乳剤層をＰＥＴフィルム上に形成させた。さらに、実施例Ａ６で得られた複合シリカ微粒子（Ｚ−６）１ｇとゼラチン１０ｇとを水１００ｇ中に分散させて、マット剤含有組成物を得た。このマット剤含有組成物を乳剤層の上にコートして試験フィルムを得た。なお、マット剤の使用量は、０．０２５ｇ／ｍ² であった。
【００７１】
上記試験フィルムをテストパターン露光後、常法で現像すると、良好な画像が得られた。さらに、以下の方法でアンチブロッキング性およびマット剤保持特性を評価した。
（アンチブロッキング性）
現像前の試験フィルムを５枚重ねて、２５℃で１週間静置後、それぞれの試験フィルムのはがれ具合を調べた。試験フィルムがきれいにはがれたものを○、ややはがれにくいものを△、はがれにくいものを×と判定した。
（マット剤保持特性）
現像前の試験フィルムを幅５ｃｍ、長さ３０ｃｍに切って、直径１ｃｍのステンレスシャフトに巻きつけた後、１ｃｍ／ｓｅｃの速度でシャフトを転がし、フィルムをはがした。この操作を１０回繰り返した後、光学顕微鏡でフィルム上にあるマット剤の量を調べた。マット剤がほとんど残っているものを○、逆に、マット剤がほとんど残っていないものを×、これらの中間のものを△と判定した。
【００７２】
上記実施例Ｃ１の試験フィルムのアンチブロッキング性およびマット剤保持特性は、いずれも○であった。
（比較例Ｃ１）
実施例Ａ６で得られた複合シリカ微粒子（Ｚ−６）に代えて、（株）日本触媒製球状シリカ微粒子粉体「シーホスター ＫＥ−Ｐ１００」を用いること以外は、実施例Ｃ１と同様にして、比較試験フィルムを得た。試験フィルムをテストパターン露光後、常法で現像すると、良好な画像が得られた。さらに、そのアンチブロッキング性は○であるが、マット剤保持特性は△であった。
【００７３】
【発明の効果】
本発明の複合シリカ微粒子は、マトリックス樹脂に対して優れた親和性を有し、物性にバラツキがない複合シリカ微粒子であり、本発明の複合シリカ微粒子の製造方法は、この複合シリカ微粒子を容易に製造することができる。
本発明の複合シリカ微粒子分散体は、複合シリカ微粒子を凝集させることなく、分散した状態で扱え、取扱性に優れる。
【００７４】
本発明のプラスチックフィルムは、複合シリカ微粒子の脱落がなくて、十分な滑り性を有し、耐摩耗性に優れたものである。したがって、プラスチックフィルムを、磁気テープ、光学写真フィルム、コンデンサーフィルム、熱転写印刷用フィルム、包装用フィルム等に用いることができ、中でも、磁気テープ用プラスチックフィルムでは、優れた磁気特性や走行性が実現できる。
【００７５】
本発明のマット剤は、優れたアンチブロッキング性を付与でき、容易に脱落しない。さらに、このマット剤をハロゲン化銀感光材料に用いると、画像特性、安定性等を付与することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to fillers used for films, molding materials, paints, fibers, photosensitive materials, etc., composite silica fine particles useful as matting agents, surface modifiers, solid lubricants, etc., production methods and dispersions thereof, The present invention relates to improvement of applications such as plastic films.
[0002]
[Prior art]
  Conventionally, various inorganic fine particles have been used as matting agents for the purpose of imparting antiblocking properties to various plastic film slipping agents, photosensitive materials, various plastic films and the like. In these applications, the smaller the contact area between the inorganic fine particles and the contact surface with which the inorganic fine particles are in contact, the more effective, and the shape of the inorganic fine particles is preferably spherical. However, the inorganic fine particles generally have a low affinity with the matrix resin constituting the plastic film and the binder resin used for fixing the matting agent.TheIt was difficult to fix inorganic fine particles with a matrix resin and a binder resin (hereinafter, “matrix resin and binder resin” may be referred to as “matrix resin or the like”). Furthermore, when the shape is spherical, there is a problem that the contact area with the matrix resin or the like becomes small and easily drops off from these.
[0003]
In order to solve the problem of the affinity between the inorganic fine particles and the matrix resin, the following composite method has been proposed.
For example, JP-A-3-271114 discloses that silica fine particles having a particle diameter of 5 to 300 nm are combined with a silyl etherified polymer. Tsubokawa et al. Introduced a polymerizable functional group or a polymerization initiating group on the surface of a silica fine particle having a particle diameter of several tens of nanometers obtained by a gas phase method, and then radically polymerized these groups, or a silyl group on the silica fine particle. It has been reported that an organic polymer is grafted onto the surface of silica fine particles by reacting a contained polymer coupling agent ("Surface" Vol. 28, No. 4, pp. 286-298, 1990). In Japanese Patent Laid-Open No. 5-115772, a polymerizable functional group is introduced into the surface of a silica fine particle obtained by a gas phase method having a particle diameter of several tens of nanometers, and then emulsion polymerization is carried out to make the surface of the silica fine particle a polymer. Grafting is described. Japanese Patent Application Laid-Open No. 4-180921 describes a method in which a colloidal silica surface having a particle diameter of 10 to 5000 nm is previously treated with a coupling agent and then combined with an acid group-containing polymer. Yoshinaga et al. Reported an example in which monodispersed silica fine particles are compounded with an alkoxysilyl group-containing polymer (“Journal of the Fiber Society”, Vol. 49, No. 3, pp. 130-136, 1993).
[0004]
[Problems to be solved by the invention]
As a result of the trials of the above-mentioned publication methods and literature-combining methods, the inventors of the present invention need to perform a drying process after the compounding. Since it is difficult to control the processing conditions accurately, it was found that the composite fine particles were agglomerated and cross-linked between the composite fine particles due to the organic polymer, resulting in variations in the particle size of the composite fine particles and low reproducibility. .
[0005]
Accordingly, an object of the present invention is to provide composite silica fine particles having excellent affinity for a matrix resin and the like and having no variation in physical properties, and a method for easily producing the composite silica fine particles.
Another object of the present invention is to provide a composite silica fine particle dispersion having excellent handleability.
[0006]
Yet another object of the present invention is to provide a plastic film that does not drop off the composite silica fine particles, has sufficient slipperiness, and is excellent in wear resistance.
Yet another object of the present invention is to provide a matting agent that imparts excellent antiblocking properties and does not easily fall off.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the inventors of the present invention do not need to perform a drying step when the silica fine particles are compounded with a specific organic polymer. Obtaining the knowledge that it can be produced, the present invention has been reached.
[0008]
  That is, the method for producing the composite silica fine particles of the present invention comprises:There are alkoxy groups on the surfaceA method for obtaining composite silica fine particles by compositing spherical silica fine particles with an organic polymer, wherein the compounding step comprises at least one organic chain and one per molecule in a dispersion in which the spherical silica fine particles are dispersed. And at least one Si-OR in the polysiloxane group¹Group (R¹Is at least one group selected from a hydrogen atom, an alkyl group and an acyl group, wherein the alkyl group and the acyl group may be substituted; R¹When there are two or more in one molecule, a plurality of R¹May be different from each other. ) -Containing organic polymer (P) is hydrolyzed and condensed to form a composite of the spherical silica fine particles.
[0009]
The composite silica fine particles of the present invention are composite silica fine particles obtained by the above production method.
The composite silica fine particle dispersion of the present invention is a dispersion formed by dispersing the composite silica fine particles in a dispersion.
The plastic film of the present invention is a film in which the composite silica fine particles are dispersed in a matrix resin.
[0010]
The matting agent of the present invention comprises the composite silica fine particles.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
[Composite Silica Fine Particles and Production Method Thereof]
The method for producing composite silica fine particles of the present invention is a method of obtaining composite silica fine particles by compositing spherical silica fine particles with an organic polymer, and this compounding step is performed in a dispersion liquid in which the spherical silica fine particles are dispersed. It is a step of complexing the spherical silica fine particles by hydrolyzing and condensing the polymer (P).
[0012]
The spherical silica fine particles used in the present invention are not particularly limited as long as the shape is spherical. The spherical shape referred to in the present invention means a true spherical shape or a shape close to a spherical shape such as an egg. For example, the aspect ratio of the particles (ratio of the shortest diameter to the longest diameter of the particles) is in the range of 0.5-2. Say something. When the aspect ratio of the particles is 0.7 to 1.5, the slipperiness of the resulting plastic film containing the composite silica fine particles is improved, or when the resulting composite silica fine particles are used as a matting agent, excellent antiblocking properties Is preferable.
[0013]
The particle size of the spherical silica fine particles is not particularly limited, and those having any particle size can be used, but those having an average particle size of 5 nm to 10 μm are preferable from the viewpoint of easy control of the reaction in the composite step, More preferably, it is 0.1-10 micrometers, Most preferably, it is 0.3-5 micrometers.
The method for producing the spherical silica fine particles is not particularly limited. For example, the spherical silica fine particles can be obtained by any of the melting method, the melt spraying method, the precipitation method, the alkoxide method, the suspension method, the interfacial polymerization method, the neutralization method, and the like. May be used. Among them, spherical silica fine particles obtained by an alkoxide method using tetramethoxysilane or the like as a raw material are preferable because many alkoxy groups that easily react with the organic polymer (P) described later are present on the surface of the spherical silica fine particles.
[0014]
The particle size distribution of the spherical silica fine particles is not particularly limited, but the coefficient of variation of the particle size is preferably 50% or less, more preferably 40% or less, and most preferably 30% or less. When the composite silica fine particles obtained using spherical silica fine particles having a wide particle size distribution with a particle size variation coefficient exceeding 50% are included as a filler in a molded product such as a plastic film, the surface smoothness of the molded product, Physical properties such as slipperiness may be reduced. Moreover, even if the obtained composite silica fine particles are used as a matting agent, sufficient antiblocking properties may not be imparted.
[0015]
The spherical silica fine particles may contain other inorganic oxides other than silica. However, because of the availability of the spherical silica fine particles, the content of the other inorganic oxides is 20% by weight of the entire spherical silica fine particles. % Or less, more preferably 10% by weight or less, and most preferably 5% by weight or less.
The spherical silica fine particles may contain an organic group or a hydroxyl group. The organic group here is at least one selected from an alkyl group having 20 or less carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group. The content of the organic group contained in the spherical silica fine particles is preferably 10% by weight or less, more preferably 5% by weight or less, and most preferably 2% by weight or less of the entire spherical silica fine particles.
[0016]
The organic polymer (P) used in the present invention is composed of an organic chain and a polysiloxane group, and has at least one polysiloxane group per molecule, and at least one Si-OR in the polysiloxane group.¹It has a structure containing a group. In the organic polymer (P), the structure of the organic chain is not particularly limited. The organic polymer (P) has a function of imparting excellent affinity for the matrix resin to the spherical silica fine particles. The bonding form between the polysiloxane group and the organic chain is a Si—C bond. Here, if the bond form is a Si—O—C bond or the like, this bond form may be easily cleaved by hydrolysis, exchange reaction, or the like.
[0017]
The structure of the organic polymer (P) is not particularly limited as long as it is soluble in an organic solvent or water described later. For example, a polymer in which a polysiloxane group is grafted to an organic chain, or a polysiloxane group is an organic chain. Polymers bonded to one or both of the ends, or polymers in which a plurality of linear or branched organic chains (multiple organic chains may be the same or different) with a polysiloxane group as the core Is mentioned.
[0018]
Here, the organic chain is a portion other than the polysiloxane group in the organic polymer (P). The element constituting the main chain in the organic chain is mainly composed of carbon atoms, the content thereof occupies 50 to 100 mol% of the entire organic chain, and the balance is N, O, S, Si, P, etc. The element occupied by these elements is preferable because it can be easily obtained. Specific examples of the resin constituting the organic chain include, for example, (meth) acrylic resin; polystyrene; polyvinyl acetate; polyolefin such as polyethylene and polypropylene; polyvinyl chloride; polyvinylidene chloride; polyester such as polyethylene terephthalate; And a partially modified resin. Among them, it is preferable that the resin constituting the organic chain is at least one selected from (meth) acrylic resins and polyesters because the organic polymer (P) can be easily produced.
[0019]
Si-OR¹R in the group¹The O group is a functional group that can be hydrolyzed and / or condensed, and is at least one per molecule of the organic polymer (P). R¹The average number of O groups is preferably 5 or more, and more preferably 20 or more. R¹As the number of O groups increases, the number of reaction points when the organic polymer (P) is hydrolyzed / condensed increases, and the bond with the spherical silica fine particles can be further strengthened. Where R¹Is at least one group selected from a hydrogen atom, an alkyl group and an acyl group, and the alkyl group and the acyl group are groups which may be substituted. The carbon number of the alkyl group or acyl group is not particularly limited, but R¹An alkyl group or an acyl group having 1 to 5 carbon atoms is preferable in order that the hydrolysis rate of the O group is high and composite silica fine particles can be easily and efficiently produced. Examples of the alkyl group having 1 to 5 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, and pentyl group. Examples of the acyl group having 1 to 5 carbon atoms include acyl groups such as an acetyl group and a propionyl group. Examples of the substituted alkyl group and the substituted acyl group include, for example, one or two or more hydrogen atoms of the alkyl group or acyl group, for example, an alkoxy group such as a methoxy group or an ethoxy group; Group, an acyl group such as propionyl group; and a group substituted by halogen such as chlorine and bromine. R¹When there are two or more in one molecule, a plurality of R¹May be the same or different. Above all, R¹Is preferably at least one selected from a hydrogen atom, a methyl group and an ethyl group, and most preferably a methyl group. This is R¹This is because the O group hydrolysis / condensation reaction rate is further increased, and composite silica fine particles can be produced easily and efficiently.
[0020]
The polysiloxane group is R¹Si-OR in which O group is bonded to Si atom¹It is a group in which one or more groups are included and two or more Si atoms are connected in a linear or branched manner by a polysiloxane bond (Si—O—Si bond). The number of Si atoms of the polysiloxane group is not particularly limited, but the above-mentioned R¹In terms of being able to contain a large amount of O groups, the average number per polysiloxane group is preferably 3 or more, more preferably 7 or more, and most preferably 11 or more. Examples of such polysiloxane groups include polymethylmethoxysiloxane groups, polyethylmethoxysiloxane groups, polymethylethoxysiloxane groups, polyethylethoxysiloxane groups, polyphenylmethoxysiloxane groups, polyphenylethoxysiloxane groups, and the like. .
[0021]
Furthermore, the Si atom in the polysiloxane group is bonded to an organic chain, and other than the polysiloxane bond (Si—O—Si bond), R¹It is preferably bonded only to the O group. In such a case, the ionicity of Si atoms is further increased, resulting in R¹O-group hydrolysis / condensation rate becomes faster, composite silica fine particles can be produced easily and efficiently, more reactive sites in organic polymer (P), and excellent affinity for matrix resin This is because the property can be imparted to the composite silica fine particles. Examples of such a polysiloxane group include a polydimethoxysiloxane group, a polydiethoxysiloxane group, a polydiisopropoxysiloxane group, and a poly n-butoxysiloxane group.
[0022]
The molecular weight of the organic polymer (P) is not particularly limited, but the number average molecular weight is preferably 200,000 or less, more preferably 50,000 or less. If the molecular weight is too high, it may not dissolve in the dispersion described later.
The organic polymer (P) can be produced by a conventionally known method, and examples thereof include, but are not limited to, the following methods (1) to (4).
[0023]
(1) After radical (co) polymerizing a radical polymerizable monomer in the presence of a silane coupling agent having a double bond group or a mercapto group, the obtained (co) polymer and a silane compound (H ) And / or a derivative thereof.
(2) A cohydrolyzed product or condensate obtained by cohydrolyzing / condensing a silane coupling agent having a double bond group or a mercapto group with a silane compound (H) and / or a derivative thereof described later. (Hereinafter, abbreviated as polymerizable polysiloxane). A method of radical (co) polymerizing a radically polymerizable monomer in the presence of.
[0024]
(3) After reacting a silane coupling agent having a reactive group such as a double bond group, amino group, epoxy group or mercapto group with a polymer having a group capable of reacting with the reactive group, A method of cohydrolyzing and condensing the obtained polymer and a silane compound (H) and / or a derivative thereof described later.
(4) After co-hydrolyzing / condensing a silane coupling agent having a reactive group such as a double bond group, amino group, epoxy group, mercapto group and the silane compound (H) and / or its derivative described later. A method of reacting the obtained polymer having a group capable of reacting with the reactive group with a cohydrolyzate or condensate having the reactive group.
[0025]
Among the above, (2) is preferable in that the organic polymer (P) can be obtained more easily.
Examples of the silane coupling agent having a reactive group such as a double bond group, an amino group, an epoxy group, and a mercapto group mentioned above include, for example, vinyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and aminopropyl. Examples include trimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, glycidoxypropyltrimethoxysilane, mercaptomethyltrimethoxysilane, mercaptopropyltrimethoxysilane, and the like.
[0026]
Examples of the silane compound (H) include acyloxysilane compounds such as methyltriacetoxysilane, dimethyldiacetoxysilane, trimethylacetoxysilane, and tetraacetoxysilane; tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane. , Alkoxysilane compounds such as methyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, dimethoxymethylphenylsilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, dimethoxydiethoxysilane, etc. It is done. Specific examples of the silane compound (H) derivative include hydrolysis / condensation products of the silane compound (H).
[0027]
  Of the silane compounds (H), alkoxysilane compounds are particularly preferred because they are readily available as raw materials. Further, when the silane compound (H) and its derivative are a tetraalkoxysilane compound and its derivative, the hydrolysis / condensation rate is high, and the surface of the spherical silica fine particles can be easily and efficiently combined to produce composite silica fine particles.For,preferable.
[0028]
In the method for producing composite silica fine particles of the present invention, spherical silica fine particles are combined in a dispersion liquid in which spherical silica fine particles are dispersed to obtain composite silica fine particles. The dispersion in which the spherical silica fine particles are dispersed contains water as an essential component and may contain an organic solvent described later. The composition is not particularly limited, but it is necessary that the composition dissolves the organic polymer (P). Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, acetic acid Esters such as ethylene glycol monobutyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Ethers such as tetrahydrofuran, dioxane, ethyl ether, di-n-butyl ether; Methanol, ethanol, isopropyl alcohol, n-butanol, ethylene Alcohols such as glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether; methylene chloride Include halogenated hydrocarbons such as chloroform and the like, may be used by mixing two or more of these. Among these, it is preferable that the organic solvent has at least one selected from alcohols, ketones, and ethers as an essential component because it is mixed with water to form a uniform mixed solution.
[0029]
As a catalyst used when hydrolyzing and condensing an organic polymer (P), a basic catalyst is preferable, and this is Si-OR in organic polymer (P).¹This is because the group conversion rate can be further increased, and the organic polymer can be more strongly bonded to the surface of the spherical silica fine particles.
Examples of the basic catalyst include ammonia; organic amine compounds such as triethylamine and tripropylamine; sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide Alkali metal compounds such as basic ion exchange resins and the like, and a mixture of two or more of these may be used. Among these, it is preferable that the basic catalyst is ammonia and / or an organic amine compound because it can be easily removed after the complexation.
[0030]
The blending ratio of the spherical silica fine particles, the organic polymer (P), the organic solvent, the basic catalyst, and the water, which are raw materials for the hydrolysis / condensation, is not particularly limited, but is preferably the following blending ratio. .
The blending ratio of the spherical silica fine particles is 0.1 to 30% by weight with respect to the total amount of each raw material component such as the spherical silica fine particles, the organic polymer (P), the organic solvent, the basic catalyst, and water. It is preferable because self-condensation between organic polymers (P) is prevented, more preferably 0.5 to 25% by weight, and most preferably 1 to 20% by weight.
[0031]
The blending ratio of the organic polymer (P) is preferably 0.01 to 60% by weight with respect to the total amount of the raw material components, because self-condensation between the organic polymers (P) is prevented, and more preferably, the blending ratio of the organic polymer (P) is 0.8. 1 to 50% by weight, most preferably 0.2 to 20% by weight.
Regarding the weight ratio of the organic polymer (P) to the spherical silica fine particles (organic polymer (P) / spherical silica fine particles), for example, 0.01 to 1, the organic polymer (P) is applied to the surface of the spherical silica fine particles. It is preferable because it can be efficiently combined and combined to prevent self-condensation of the organic polymer (P). More preferably, it is 0.05-0.7, Most preferably, it is 0.1-0.5. When the weight ratio is larger than 1, the organic polymers (P) may self-condense, and a condensate of the organic polymer (P) may be by-produced. On the other hand, when the weight ratio is smaller than 0.01, the organic polymer (P) is too small, and the spherical silica fine particles are difficult to be combined, and this is not sufficiently performed. It becomes impossible to give excellent affinity for. In addition, the self-condensate obtained by self-condensing organic polymers (P) may be contained in the composite silica fine particles obtained after the composite, but in order to perform the composite more efficiently However, it is preferable to carry out hydrolysis / condensation within the above weight ratio range.
[0032]
Regarding the blending ratio of the organic solvent, for example, when it is 0 to 99.9% by weight with respect to the total amount of the raw material components, the spherical silica fine particles are uniformly dispersed in the dispersion, and the organic polymer (P) is dispersed in the dispersion. Therefore, it is preferable to be 20 to 99% by weight, and most preferable to be 40 to 99% by weight.
Regarding the blending ratio of the basic catalyst, for example, 0.01 to 20% by weight relative to the total amount of the raw material components, Si—OR in the organic polymer (P)¹It is preferable because the group can be sufficiently hydrolyzed and condensed, more preferably 0.05 to 10% by weight, and most preferably 0.1 to 5% by weight.
[0033]
The blending ratio of water is not particularly limited as long as the organic polymer (P) can be hydrolyzed / condensed to easily composite spherical silica fine particles to produce composite silica fine particles. A larger ratio is preferable because the organic polymer (P) is easily hydrolyzed and condensed. The mixing ratio of water is, for example, Si-OR that undergoes hydrolysis and condensation.¹The molar ratio with respect to the group is 0.1 or more, preferably 2 or more, more preferably 3 or more. However, when the organic polymer (P) is insoluble in water, the mixing ratio of water is preferably 50% by weight or less, more preferably 30% by weight or less, and most preferably based on the total amount of the raw material components. 15% by weight or less.
[0034]
The method for producing composite silica fine particles of the present invention is performed by hydrolyzing and condensing the organic polymer (P) in a dispersion in which spherical silica fine particles are dispersed. The reaction temperature is usually 0 to 100 ° C., preferably 0 to 70 ° C. The reaction time is usually 5 minutes to 100 hours, and the hydrolysis / condensation is usually carried out by stirring.
[0035]
In the method for producing composite silica fine particles of the present invention, the organic polymer (P) is hydrolyzed by mixing raw material components such as spherical silica fine particles, organic polymer (P), organic solvent, basic catalyst, and water. -Condensation results in the formation of spherical silica fine particles. The method of mixing each raw material component is not particularly limited, but the respective raw material components such as spherical silica fine particles, organic polymer (P), organic solvent, basic catalyst, and water are mixed individually or sequentially. Alternatively, a mixture in which several components are mixed may be prepared in advance, and the mixture may be mixed, or a mixture in which several components are mixed may be mixed with a single component. In particular, water, which is a component necessary for hydrolyzing and condensing the organic polymer (P), may be included in advance in a dispersion in which spherical silica fine particles are dispersed, together with the organic polymer (P). Alternatively, it may be contained in the dispersion separately from the organic polymer (P), or water may be further contained after the organic polymer (P) is contained in the dispersion. Further, by-products generated by hydrolysis / condensation, catalysts, and the like may be removed by filtration or distillation.
[0036]
After compounding the spherical silica fine particles in the dispersion liquid as described above, the water and organic solvent contained in the dispersion liquid are not necessarily removed for the purpose of fixing the organic polymer (P) on the surface of the spherical silica fine particles. There is no need to dry, and the resulting composite silica fine particles are not agglomerated or crosslinked between the composite silica fine particles by the organic polymer (P), and the physical properties such as the particle diameter of the obtained composite silica fine particles do not vary.
[0037]
The composite silica fine particles obtained by the above production method may be used as a composite silica fine particle dispersion described later as they are after the composite step. You may provide the isolation process which isolate | separates a composite silica fine particle from the dispersion liquid after reaction after the composite process. As an isolation process, for example, an isolation process in which a composite silica fine particle is precipitated by adding a solvent having a low affinity with the composite silica fine particle to the manufactured dispersion liquid (dispersion) and filtered, or a dispersion after the manufacture is performed. The isolation process etc. which distill away the dispersion medium contained in the dispersion liquid after manufacture by reducing pressure or heating a liquid (dispersion) etc. are mentioned.
[0038]
The composite silica fine particles of the present invention are obtained by the above production method, and the organic polymer is fixed to the surface of the spherical silica fine particle main body through Si—O—Si bonds. Here, the spherical silica fine particle main body has a structure derived from the spherical silica fine particles, and the organic polymer has a structure derived from the organic chain in the organic polymer (P).
[0039]
The ratio of the organic polymer to the entire composite silica fine particle is not particularly limited. However, when the composite silica fine particle is included in the plastic film of the present invention described later, if the organic polymer is too small in the composite silica fine particle, the matrix resin, etc. Affinity with the resin is reduced, and fine particles come off from the surface and inside of the plastic film, resulting in a decrease in wear resistance. On the other hand, when the proportion of the organic polymer is too large, physical properties such as hardness and heat resistance, which are characteristics of silica, are lowered. For this reason, the ratio of the organic polymer is preferably 0.1 to 60% by weight, more preferably 1 to 40% by weight, and most preferably 2 to 30% by weight with respect to the entire composite silica fine particles.
[0040]
On the surface of the spherical silica fine particle main body in the composite silica fine particles, organic groups and hydroxyl groups derived from the spherical silica fine particles as the raw material may remain, and the polysiloxane groups in the organic polymer (P) as the raw material An alkoxy group therein, an organic group derived from the organic solvent used, or the like may remain.
[Composite silica fine particle dispersion]
The composite silica fine particle dispersion of the present invention is a dispersion formed by dispersing the composite silica fine particles in a dispersion.
[0041]
Examples of the dispersion medium constituting the dispersion include the organic solvent and water described above, and a mixture of the organic solvent and water may be used as the dispersion medium.
The compounding ratio of the composite silica fine particles contained in the composite silica fine particle dispersion is preferably 0.1 to 60% by weight, more preferably 0.5 to 50% by weight, and most preferably based on the whole composite silica fine particle dispersion. Is 1 to 30% by weight. When the compounding ratio of the composite silica fine particles exceeds 60% by weight, the viscosity of the dispersion becomes high and handling becomes difficult.
[0042]
As the composite silica fine particle dispersion, for example, in the above-described method for producing composite silica fine particles, the composite silica fine particles are left as they are without isolation, or after the composite silica fine particles are produced by the above production method, filtration, drying, etc. Once the composite silica fine particles are isolated and then mixed again with the dispersion medium, the composite silica fine particle dispersion obtained by the above production method is reduced in pressure, heated, etc. Some are produced by adding another dispersion medium while distilling off the dispersion medium during the production of the fine particles and substituting the dispersion medium.
[0043]
The composite silica fine particle dispersion has an advantage of high handling property because it is much less aggregated than the isolated composite silica fine particle and can be handled in a dispersed state. [Plastic film]
The plastic film of the present invention is a plastic film in which the composite silica fine particles are dispersed in a matrix resin, and includes the composite silica fine particles obtained by the above production method and the matrix resin.
[0044]
Although it does not specifically limit about matrix resin, For example, (meth) acrylic resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyester, polycarbonate, polystyrene, ethylene vinyl acetate copolymer etc. are mentioned, These Two or more kinds may be mixed and used. Among them, it is preferable that the matrix resin is a (meth) acrylic resin and / or polyester because affinity with the organic polymer in the composite silica fine particles is increased.
[0045]
The blending ratio of the composite silica fine particles contained in the plastic film is not particularly limited, but is preferably 0.001 to 10% by weight, more preferably 0.005 to 8% by weight, most preferably based on the whole plastic film. Is 0.01 to 5% by weight. When the composite silica fine particles are less than 0.001% by weight of the entire plastic film, slipping property, hardness and antiblocking property are not imparted to the plastic film. On the other hand, when it exceeds 10% by weight, it becomes difficult to obtain a plastic film by molding, and physical properties such as appearance, strength, and smoothness are deteriorated.
[0046]
Although the method for producing the plastic film is not particularly limited, for example, there are the following production methods (1) to (3).
(1) A method of producing a plastic film by forming a composition obtained by mixing a matrix resin and composite silica fine particles into a film by a molding method described later.
(2) The composition obtained by mixing the matrix resin raw material and the composite silica fine particles is reacted to convert to a composition obtained by mixing the matrix resin and the composite silica fine particles, and then the molding method described below is used. A method for producing plastic film by converting it into a film.
[0047]
(3) A method in which a film containing a matrix resin as a substrate is prepared in advance, and the surface of the film is coated with a coating agent containing composite silica fine particles.
The molding method used in the above (1) and (2) is not particularly limited. For example, molding methods such as a melt extrusion method, a co-melt extrusion method, an inflation method, a T-die method, a casting method, a calendar method, etc. Is mentioned. Further, after molding, a plastic film may be produced by performing treatments such as stretching, vapor deposition, laminating, and primer coating.
[0048]
In order to obtain a composition of matrix resin and composite silica fine particles in the above (1), first, the above-mentioned composite silica fine particle dispersion and matrix resin are mixed, and then the dispersion medium in the dispersion is removed by distillation or the like. Further, it is necessary to mix the isolated and dried composite silica fine particles with the matrix resin, and then re-disperse the composite silica fine particles in the matrix resin with an ultrasonic disperser or a homogenizer. In the above (2), since the composite silica fine particle dispersion in which the composite silica fine particles are dispersed in the matrix resin raw material is used, the removal of the dispersion medium performed in the above (1) and the redispersion of the composite silica fine particles are performed. The process to perform can be omitted.
[0049]
In the method of coating with the coating agent of (3) above, a matrix resin as a base material is molded, and a film is prepared by appropriately performing treatments such as stretching, vapor deposition, laminating, primer coating, etc. This is a method of coating with a coating agent containing composite silica fine particles. In addition, you may perform processes, such as extending | stretching, vapor deposition, and a lamination, after coat | covering with a coating agent.
[0050]
The coating agent contains composite silica fine particles as an essential component and contains an organic binder.
The organic binder is not particularly limited as long as it has a film-forming ability by itself, but is preferably compatible with the organic chain in the composite silica fine particles. For example, (meth) acrylic resin, polystyrene, polyacetic acid Vinyl, polyolefins such as polyethylene and polypropylene, polyesters such as polyvinyl chloride, polyvinylidene chloride, and polyethylene terephthalate, and copolymers thereof, and some functional groups such as amino groups, epoxy groups, hydroxyl groups, and carboxyl groups Modified resins and the like can be mentioned, and two or more of these may be mixed and used. Above all, when the organic binder is a (meth) acrylic resin and / or polyester, it has a high affinity with the organic polymer in the composite silica fine particles, and the composite silica fine particles do not fall off from the plastic film, so that sufficient slipperiness is achieved. Is preferable because it can be maintained for a long period of time.
[0051]
The coating agent may further contain a curing agent that cures the organic binder, if necessary.
The method of coating with the coating agent in the above (3) is not particularly limited, but can be performed by any method such as roller coating, gravure coating, dip coating, spray coating, and the like. Also, the drying method and drying conditions after coating are not particularly limited, and any method and conditions can be used.
[0052]
The coating agent may contain the above-mentioned organic solvent and / or water, if necessary, depending on the suitability for the above coating method and the desired film thickness.
Any of the above methods (1) to (3) may be performed, and the method is appropriately selected according to the situation. For example, when it is desired to omit the coating step (3), or when there is no apparatus used for coating, a plastic film can be obtained by either method (1) or (2). When there is no molding machine such as an extruder, a plastic film can be obtained by the method (3).
[0053]
The plastic film of the present invention has no slip of composite silica particles from the surface and the inside thereof, has sufficient slipperiness, and is excellent in abrasion resistance. For example, magnetic tape, optical photographic film, condenser film, thermal transfer printing It can be effectively used for film for packaging, packaging film and the like, and in particular, a plastic film for magnetic tape can realize excellent magnetic properties and running properties.
(Matting agent)
The matting agent of the present invention is a matting agent comprising the above-mentioned composite silica fine particles, contains the composite silica fine particles obtained by the above production method, and is useful for silver halide light-sensitive materials.
[0054]
For example, when the above-mentioned composite silica fine particles are used as a matting agent for a silver halide photosensitive material, conventionally known materials can be used as other members constituting the silver halide photosensitive material. That is, any material can be used as a substrate, resin binder, sensitizing dye, surfactant, ultraviolet absorber, plasticizer, stabilizer, hardener, thickener, etc., and halogenated by any method. Silver particles can be used. Further, if necessary, a magnetic recording layer may be provided or a magnetic powder may be used in combination.
[0055]
The matting agent of the present invention can be used in any method for any layer constituting the silver halide light-sensitive material, for example, at least one layer selected from a substrate, an undercoat layer, an intermediate layer, an emulsion layer, a protective layer and the like. .
The amount of the matting agent used is not particularly limited, but is preferably 0.002 to 2 g / m.²And more preferably 0.05 to 0.5 g / m²It is.
[0056]
The silver halide light-sensitive material obtained using the matting agent of the present invention is a good light-sensitive material because it has excellent antiblocking properties, image characteristics, and stability, and the matting agent is hardly removed.
[0057]
【Example】
Specific examples of the present invention are shown below, but the present invention is not limited to the following examples.
Polymerizable polysiloxane and organic polymer (P) were synthesized according to the following Production Examples 1 to 10, and then Examples were carried out.
(Production Example 1)
(Production of polymerizable polysiloxane (S-1))
In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 144.5 g of tetramethoxysilane, 23.6 g of γ-methacryloxypropyltrimethoxysilane, 19 g of water, 30.0 g of methanol, Amberlyst 15 (Rohm 5.0 g of a cation exchange resin manufactured by And Hearth Japan Co., Ltd. was added, and the mixture was stirred at 65 ° C. for 2 hours to be reacted. After cooling the reaction mixture to room temperature, a distillation column, a cooling tube connected to the distillation column, and an outlet are provided instead of the cooling tube, and the temperature is raised to 80 ° C. over 2 hours under normal pressure until methanol does not flow out. Hold at the same temperature. Furthermore, the reaction was further proceeded by maintaining the same temperature at 90 ° C. under a pressure of 200 mmHg until the methanol did not flow out. After cooling to room temperature again, Amberlyst 15 was filtered off to obtain polymerizable polysiloxane (S-1) having a number average molecular weight of 1800.
(Production Example 2)
(Production of organic polymer (P-1))
Stirrer, dripping port, thermometer, cooling pipe and N₂Into a 1 liter flask equipped with a gas inlet, 200 g of butyl acetate as an organic solvent was added.₂Gas was introduced and the temperature inside the flask was heated to 120 ° C. while stirring. Next, 20 g of the polymerizable polysiloxane (S-1) obtained in Production Example 1, 80 g of methyl methacrylate, 10 g of 2-ethylhexyl acrylate, 60 g of styrene, 30 g of butyl acrylate, 6.5 g of 2,2′-azobisisobutyronitrile. Was added dropwise from the dropping port over 2 hours. After the dropwise addition, stirring was continued at the same temperature for 1 hour, and then 0.4 g of 1,1′-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane was added twice every 30 minutes. Copolymerization was performed by heating for a time to obtain a solution in which an organic polymer (P-1) having a number average molecular weight of 11,000 was dissolved in butyl acetate. The solid content in the obtained solution was 49.0%.
(Production Example 3)
(Production of organic polymer (P-2))
Stirrer, dripping port, thermometer, cooling pipe and N₂In a 500 ml flask equipped with a gas inlet, 260 g of methanol was placed, and N₂Gas was introduced and the temperature inside the flask was heated to 65 ° C. while stirring. Next, 14 g of the polymerizable polysiloxane (S-1) obtained in Production Example 1, 63 g of 2-hydroxyethyl acrylate, 63 g of polyoxyethylene methacrylate, and 4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) are mixed. The solution was added dropwise from the dropping port over 2 hours. After the dropwise addition, stirring was continued at the same temperature for 1 hour, and then 0.3 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added twice every 30 minutes, followed by further heating for 2 hours for copolymerization. And a solution in which an organic polymer (P-2) having a number average molecular weight of 9,000 was dissolved in methanol was obtained. The solid content in the obtained solution was 35.0%.
(Production Examples 4 to 5)
(Production of organic polymer (P-3 to P-4))
Except having changed into the composition shown in Table 1, it carried out similarly to manufacture example 3, and obtained the solution in which the organic polymer (P-3-P-4) melt | dissolved in methanol. Table 1 shows the number average molecular weight of the obtained organic polymers (P-3 to P-4) and the solid content in the solution.
[0058]
[Table 1]

[0059]
AIBN: 2,2'-azobisisobutyronitrile
ADVN: 2,2'-azobis (2,4-dimethylvaleronitrile)
MMA: Methyl methacrylate
2-EHA: 2-ethylhexyl acrylate
St: Styrene
HEA: 2-hydroxyethyl acrylate
HEMA: 2-hydroxyethyl methacrylate
POEMA: Polyoxymethylene methacrylate
AA: Acrylic acid
S-1: Polymerizable polysiloxane (S-1)
(Production Example 6)
(Production of spherical silica fine particle dispersion solvent (D-1))
In a 1 liter four-necked flask equipped with a stirrer, two dropping ports (dropping port A and dropping port B) and a thermometer, 511 g of butyl acetate and 128 g of methanol were placed, and the internal temperature was adjusted to 20 ° C. Then, while stirring the flask, 108 g of tetramethoxysilane was dropped from the dropping port (i) and a mixed solution of 41 g of water, 14 g of 25% aqueous ammonia and 55 g of methanol was dropped from the dropping port (B) over 40 minutes. After the dropping, stirring was continued for 1 hour at the same temperature to obtain a spherical silica fine particle dispersion solvent (D-1). Table 2 shows the average particle diameter and coefficient of variation of the obtained spherical silica fine particles and the liquid composition of the spherical silica fine particle dispersion solvent (D-1).
[0060]
In addition, the average particle diameter and coefficient of variation of spherical silica fine particles and composite silica fine particles described later were measured by the following methods.
(Average particle size and coefficient of variation)
The particles were photographed with a transmission electron microscope, the diameters of arbitrary 100 particles were read, and the average was taken as the average particle diameter. In addition, the coefficient of variation was calculated by the following formula.
[0061]
Coefficient of variation (%) = (standard deviation of particle diameter) / (average particle diameter of particles)
(Production Example 7)
(Production of spherical silica fine particle dispersion solvent (D-2))
In a 1 liter Meyer flask equipped with a stirrer and an ultrasonic homogenizer, 696 g of methanol and 24 g of spherical silica fine particle powder “Seahoster KE-P100” manufactured by Nippon Shokubai Co., Ltd. were placed and subjected to ultrasonic dispersion for 1 hour. Next, 80 g of aqueous ammonia was added, and the mixture was stirred at room temperature for 1 hour to obtain a spherical silica fine particle dispersion solvent (D-2). Table 2 shows the average particle size of the spherical silica fine particles, the coefficient of variation, and the liquid composition of the spherical silica fine particle dispersion solvent (D-2) in the obtained solvent.
(Production Example 8)
(Production of spherical silica fine particle dispersion solvent (D-3))
A spherical silica fine particle-dispersed solvent (D-3) was obtained in the same manner as in Production Example 7 except that “Seahoster KE-P250” manufactured by Nippon Shokubai Co., Ltd. was used as the spherical silica fine particle powder. Table 2 shows the average particle diameter, variation coefficient, and liquid composition of the spherical silica fine particle dispersion solvent (D-3) in the obtained solvent.
(Production Example 9)
(Production of spherical silica fine particle dispersion solvent (D-4))
A 500 ml four-necked flask equipped with a stirrer, two dripping ports (dropping port a and dripping port b) and a thermometer was charged with 229 g of methanol and 36 g of 25% aqueous ammonia, and the internal temperature was adjusted to 20 ° C. did. Next, while stirring the inside of the flask, 73 g of tetramethoxysilane was dropped from the dropping port (i) and 17 g of water was dropped from the dropping port (B) over 40 minutes. After the dropping, stirring was continued for 1 hour at the same temperature to obtain a spherical silica fine particle dispersion solvent (D-4). Table 2 shows the average particle size and coefficient of variation of the obtained spherical silica fine particles and the liquid composition of the spherical silica fine particle dispersion solvent (D-4).
(Production Example 10)
(Production of spherical silica fine particle dispersion solvent (D-5))
A 1 liter Meyer flask equipped with a stirrer was charged with 688 g of methanol, 40 g of “Snowtex C” manufactured by Nissan Chemical Industries, Ltd., and 72 g of aqueous ammonia, and stirred for 1 hour to obtain a spherical silica fine particle dispersion solvent (D-5). Got. Table 2 shows the average particle diameter, variation coefficient, and liquid composition of the spherical silica fine particle dispersion solvent (D-5) in the obtained solvent.
[0062]
[Table 2]

[0063]
(Example A1)
(Production of composite silica fine particle (Z-1) dispersion)
350 g of the spherical silica fine particle dispersion solvent (D-1) obtained in Production Example 6 was placed in a 500 ml four-necked flask equipped with a stirrer, a dripping port, and a thermometer, and the internal temperature was adjusted to 20 ° C. Next, while stirring the inside of the flask, a mixed solution of 4.5 g of the butyl acetate solution of organic polymer (P-1) obtained in Production Example 2 and 4.5 g of butyl acetate was added dropwise over 20 minutes. After dropping, stirring was continued for 1 hour at the same temperature. Further, under a pressure of 110 mmHg, the temperature inside the flask was raised to 100 ° C., and ammonia, methanol, water, and butyl acetate were distilled off until the solid content was 25%, and the composite silica fine particles (Z-1) were dispersed in butyl acetate. Got the body. Table 3 shows the average particle size, coefficient of variation, and silica concentration in the fine particles of the obtained composite silica fine particles (Z-1).
[0064]
In addition, the average particle diameter and coefficient of variation of the composite silica fine particles were measured by the method described above. Further, the silica concentration in the composite silica fine particles was measured by the following method.
(Silica concentration in composite silica fine particles)
Elemental analysis was performed on the composite silica fine particle powder obtained by drying the composite silica fine particle dispersion, and the ash content was calculated as silica.
(Example A2)
(Production of composite silica fine particle (Z-2) dispersion)
380 g of the spherical silica fine particle dispersion solvent (D-2) obtained in Production Example 7 was placed in a 500 ml four-necked flask equipped with a stirrer, a dripping port, and a thermometer, and the internal temperature was adjusted to 20 ° C. Next, while stirring the inside of the flask, a mixed solution of 4 g of a methanol solution of the organic polymer (P-2) obtained in Production Example 3 and 4 g of methanol was added dropwise over 20 minutes. After dropping, stirring was continued for 1 hour at the same temperature. Further, under a pressure of 60 mmHg, the temperature inside the flask was raised to 125 ° C., 103 g of ethylene glycol was added dropwise while distilling off ammonia, methanol and water, and the mixture was concentrated until the solid content became 10%. -2) ethylene glycol dispersion was obtained. Table 3 shows the average particle size and coefficient of variation of the obtained composite silica fine particles (Z-2), and the silica concentration in the fine particles.
(Example A3)
(Production of composite silica fine particle (Z-3) dispersion)
In a 500 ml four-necked flask equipped with a stirrer, a dripping port and a thermometer, 380 g of the spherical silica fine particle dispersion solvent (D-3) obtained in Production Example 8 was placed, and the internal temperature was adjusted to 20 ° C. Next, a mixture of 9.2 g of a methanol solution of the organic polymer (P-3) obtained in Production Example 4 and 9.2 g of methanol was added dropwise over 20 minutes while stirring the flask. After dropping, stirring was continued for 1 hour at the same temperature. Further, under a pressure of 60 mmHg, the temperature inside the flask was raised to 125 ° C., 103 g of ethylene glycol was added dropwise while distilling off ammonia, methanol and water, and the mixture was concentrated until the solid content became 10%. -3) ethylene glycol dispersion was obtained. Table 3 shows the average particle size, coefficient of variation, and silica concentration in the resulting composite silica fine particles (Z-3).
(Example A4)
(Production of composite silica fine particle (Z-4) dispersion)
350 g of the spherical silica fine particle dispersion solvent (D-4) obtained in Production Example 9 was placed in a 500 ml four-necked flask equipped with a stirrer, a dripping port, and a thermometer, and the internal temperature was adjusted to 20 ° C. Next, while stirring the inside of the flask, a mixed solution of 16 g of a methanol solution of the organic polymer (P-4) obtained in Production Example 5 and 16 g of methanol was dropped over 20 minutes. After dropping, stirring was continued for 1 hour at the same temperature. Further, under a pressure of 60 mmHg, the temperature inside the flask was raised to 125 ° C., 257 g of ethylene glycol was added dropwise while distilling off ammonia, methanol, and water, and the mixture was concentrated until the solid content became 10%. -4) ethylene glycol dispersion was obtained. Table 3 shows the average particle size, coefficient of variation, and silica concentration in the fine particles of the obtained composite silica fine particles (Z-4).
(Example A5)
(Production of composite silica fine particle (Z-5) dispersion)
380 g of the spherical silica fine particle dispersion solvent (D-5) obtained in Production Example 10 was placed in a 500 ml four-necked flask equipped with a stirrer, a dripping port, and a thermometer, and the internal temperature was adjusted to 20 ° C. Next, while stirring the inside of the flask, a mixed solution of 1.5 g of a methanol solution of the organic polymer (P-2) obtained in Production Example 3 and 6.5 g of methanol was added dropwise over 20 minutes. After dropping, stirring was continued for 1 hour at the same temperature. Further, under a pressure of 60 mmHg, the temperature inside the flask was raised to 125 ° C., 34 g of ethylene glycol was added dropwise while distilling off ammonia, methanol, and water, and the mixture was concentrated to a solid content of 10%. The ethylene glycol dispersion of -5) was obtained. Table 3 shows the average particle size, coefficient of variation, and silica concentration in the fine particles of the obtained composite silica fine particles (Z-4).
(Example A6)
(Production of composite silica fine particles (Z-6))
In a 500 ml four-necked flask equipped with a stirrer, a dropping port, and a thermometer, 330 g of the spherical silica fine particle dispersion solvent (D-2) obtained in Production Example 7 was placed, and the internal temperature was adjusted to 20 ° C. Next, while stirring the inside of the flask, a mixed solution of 30 g of a methanol solution of the organic polymer (P-2) obtained in Production Example 3 and 30 g of methanol was added dropwise over 40 minutes. After dropping, stirring was continued for 1 hour at the same temperature. Further, under normal pressure, the temperature inside the flask was raised to 70 ° C., ammonia, methanol and water were distilled off, and the mixture was concentrated until the solid content became 30%. Furthermore, it hold | maintained at 120 degreeC under the pressure of 50 mmHg for 2 hours in the vacuum dryer, and the dried body of the composite silica fine particle (Z-6) was obtained. Table 3 shows the average particle size and coefficient of variation of the obtained composite silica fine particles (Z-6), and the silica concentration in the fine particles.
[0065]
[Table 3]

[0066]
(Comparative Example A1)
(Surface treatment of spherical silica fine particles)
380 g of the spherical silica fine particle dispersion solvent (D-2) obtained in Production Example 7 was placed in a 500 ml four-necked flask equipped with a stirrer, a dripping port, and a thermometer, and the internal temperature was adjusted to 20 ° C. Then, a mixture of 4 g of methyltrimethoxysilane and 4 g of methanol was added dropwise over 30 minutes while stirring the flask. After dropping, stirring was continued for 1 hour at the same temperature. In the obtained liquid, fine particles were newly generated in addition to the spherical silica fine particles obtained in Production Example 7, and the surface treatment of the spherical silica fine particles could not be performed well.
(Comparative Example A2)
(Surface treatment of spherical silica fine particles)
In a 1 liter Meyer flask equipped with a stirrer and an ultrasonic homogenizer, 696 g of methanol and 24 g of spherical silica fine particle powder “Seahoster KE-P100” manufactured by Nippon Shokubai Co., Ltd. were placed and subjected to ultrasonic dispersion for 1 hour. Next, 0.2 g of methyltrimethoxysilane was added, and the mixture was stirred at room temperature for 1 hour. It was heat-dried at 120 ° C. for 24 hours under a pressure of 50 mmHg in a vacuum dryer to obtain a surface treated product powder (Z′-1) of spherical silica fine particles.
(Comparative Example A3)
(Production of spherical silica fine particle dispersion)
A 300 ml Meyer flask equipped with a stirrer and an ultrasonic homogenizer was charged with 20 g of spherical silica fine particle powder “Seahoster KE-P100” manufactured by Nippon Shokubai Co., Ltd. and 180 g of ethylene glycol, and subjected to ultrasonic dispersion for 1 hour. Subsequently, stirring was performed at room temperature for 1 hour to obtain spherical silica fine particle ethylene glycol dispersion.
(Comparative Example A4)
(Production of spherical silica fine particle dispersion)
Spherical silica fine particle ethylene glycol dispersion was obtained in the same manner as in Comparative Example A1 except that the surface treated product powder (Z′-1) of the spherical silica fine particle obtained in Comparative Example A2 was used.
(Example B1)
(Manufacture of plastic film (F-1))
1 g of a butyl acetate dispersion (Z-1) of composite silica fine particles obtained in Production Example 1, 15 g of polyester resin “Alloplats BO-110” manufactured by Nippon Shokubai Co., Ltd., and 400 g of butyl acetate were mixed to prepare a coating solution. This coating solution was applied to one side of a polyethylene terephthalate film with a bar coater and dried at room temperature for 20 minutes and at 140 ° C. for 20 minutes. Table 4 shows the test results on the slipperiness (dynamic friction coefficient) and wear resistance of the obtained plastic film (F-1) and the affinity between the composite silica fine particles in the plastic film and the resin constituting the film. The resulting plastic film had good sliding properties, wear resistance and affinity.
[0067]
The plastic film was evaluated by the following method.
(Dynamic friction coefficient)
The film was cut into 200 × 100 mm and measured with the following apparatus.
HEIDON continuous load type surface property measuring machine TYPE: HEIDON-22 (Abrasion resistance)
A 20 g load was applied to both ends of a film having a length of 40 cm and a width of 15 mm, and a stainless steel pin having a bending angle of 150 degrees and a diameter of 5 mm was reciprocated 200 times and rubbed.
[0068]
  The appearance was observed for the presence or absence of scratches, and those having almost no scratch were marked with ◯, those with many scratches were marked with ×, and those with an intermediate score were marked with Δ.
(Affinity)
  After examining the abrasion resistance, the surface of the film was observed with a scanning electron microscope. The case where there was almost no dropout of the particles was indicated as ◯, the case where there was much dropout of the particles was indicated as ×, and the intermediate one was indicated as Δ.
(Example B2)
(Manufacture of plastic film (F-2))
  1 g of butyl acetate dispersion (Z-1) of composite silica fine particles obtained in Production Example 1, 15 g of acrylic resin “Allotane 2060” manufactured by Nippon Shokubai Co., Ltd., isocyanate curing agent “Sumijoule N” manufactured by Sumitomo Chemical Co., Ltd. −3500 ”2.5 g and butyl acetate 400 g were mixed to prepare a coating solution. This coating solution was applied to one side of a polyethylene terephthalate film with a bar coater and dried at room temperature for 30 minutes and at 80 ° C. for 40 minutes. Table 4 shows the test results on the slipperiness (dynamic friction coefficient), wear resistance and affinity of the obtained plastic film (F-2).
(Example B3)
(Manufacture of plastic film (F-3))
  1 g of butyl acetate dispersion (Z-1) of composite silica fine particles obtained in Production Example 1, 15 g of “Udable S-5140SPL” acrylic resin manufactured by Nippon Shokubai Co., Ltd., and 400 g of butyl acetate were mixed to prepare a coating solution. This coating solution was applied to one side of a polyethylene film with a bar coater and dried at room temperature for 20 minutes and at 60 ° C. for 40 minutes. Table 4 shows the test results on the slipperiness (dynamic friction coefficient), wear resistance, and affinity of the obtained plastic film (F-3).
(Comparative Example B1)
(Manufacture of plastic film (F′-1))
  Japan Catalyst Co., Ltd. spherical silica fine particle powder "Seahoster KE-P100" 0.5g, Japan Catalyst Co., Ltd. polyester resin "Alloplats BO-110" 30g, butyl acetate 800g was mixed, and then ultrasonically dispersed for 30 minutes. Coating solution. This coating solution was applied to one side of a polyethylene terephthalate film with a bar coater and dried at room temperature for 20 minutes and at 140 ° C. for 20 minutes. Table 4 shows the test results on the slipperiness (dynamic friction coefficient), wear resistance and affinity of the obtained plastic film (F′-1).
(Comparative Example B2)
(Manufacture of plastic film (F'-2))
  A plastic film (F′-2) is obtained in the same manner as in Comparative Example B1, except that 0.5 g of the surface-treated product powder (Z′-1) of the spherical silica fine particles obtained in Comparative Example A2 is used as the spherical silica fine particles. It was. Table 4 shows the test results on the slipperiness (dynamic friction coefficient), wear resistance and affinity of the obtained plastic film (F'-2).
(Example B4)
(Manufacture of plastic film (F-4))
  0.04 g of manganese acetate tetrahydrate as a catalyst was added to 100 g of dimethyl terephthalate and 70 g of ethylene glycol to a 500 ml four-necked flask equipped with a distillation column connected with a stirrer, a thermometer, a condenser and an outlet. The temperature was raised to 230 ° C. and methanol was distilled off to conduct a transesterification reaction. Next, 3 g of an ethylene glycol dispersion of composite silica fine particles (Z-2) obtained in Example A2 and 0.03 g of antimony trioxide were added with stirring, and then the temperature was raised to 280 ° C. under a pressure of 1 mmHg. Condensation was performed to obtain a polyester resin. This polyester resin was extruded into a sheet with an extruder set at 290 ° C., then stretched 3.5 times in the machine direction at 90 ° C., then stretched 4 times in the transverse direction at 100 ° C., and heat treated at 210 ° C. for 10 seconds. To obtain a plastic film (F-4). The resulting plastic film had good sliding properties and wear resistance. Table 4 shows the test results on the slipperiness (dynamic friction coefficient), wear resistance and affinity of the obtained plastic film (F-4).
(Examples B5 to B7)
(Manufacture of plastic films (F-5 to F-7))
  Plastic films (F-5 to F-7) were obtained in the same manner as in Example B4, except that the composite silica fine particle ethylene glycol dispersion shown in Table 4 was used. Table 4 shows the test results of the obtained plastic films (F-5 to F-7) on slipperiness (coefficient of dynamic friction), wear resistance and affinity.
(Comparative Examples B3 to B4)
(Manufacture of plastic films (F'-3 to F'-4))
  Plastic films (F′-3 to F′-4) were obtained in the same manner as in Example B4 except that the spherical silica fine particle ethylene glycol dispersion obtained in Comparative Examples A3 and A4 was used. Table 4 shows the test results of the obtained plastic films (F′-3 to F′-4) on slipperiness (dynamic friction coefficient), wear resistance and affinity.
(Example B8)
(Manufacture of plastic film (F-8))
  To 97 parts of polypropylene (melt flow index (MI) 2 g / 10 min, heptane soluble content 3%) 97 parts of the composite silica fine particles (Z-6) obtained in Example A6 was blended with 3 parts. The mixture was kneaded at 230 ° C. with a Banbury mixer to obtain pellets. Next, 10 parts of the pellets and 90 parts of the polypropylene were mixed, extruded into a sheet shape with an extruder set at 260 ° C., then stretched 5 times in the longitudinal direction at 175 ° C., and then at the same temperature.Next toThe film was stretched 9 times in the direction to obtain a plastic film (F-8). Table 4 shows the test results on the slipperiness (dynamic friction coefficient), wear resistance and affinity of the obtained plastic film (F-8).
(Example B9)
(Manufacture of plastic film (F-9))
  Low density polyethylene (melt flow index (MI) 2g / 10min, density 0.92g / cm ³ ) To 95 parts, 5 parts of the dried composite silica fine particles (Z-6) obtained in Example 6 was blended and kneaded at 220 ° C. with a Banbury mixer to obtain pellets. Next, 8 parts of the pellets and 92 parts of the polyethylene were mixed and extruded into a sheet form from a T-die with an extruder set at 200 ° C. to obtain a plastic film (F-9). Table 4 shows the test results on the slipperiness (dynamic friction coefficient), wear resistance and affinity of the obtained plastic film (F-9).
[0069]
[Table 4]

[0070]
(Example C1)
Silver chloride crystals having an average particle size of 0.3 μm were treated with a 0.05N potassium iodide solution, and the resulting precipitate was purified. After redissolving, emulsion treated by mixing with chloroauric acid, 4-hydroxy-6-methyl-1,3,3a-7-tetrazidene, surfactant and hardener were prepared. . This emulsion was coated on a polyethylene terephthalate film (PET film) to form an emulsion layer on the PET film. Further, 1 g of the composite silica fine particles (Z-6) obtained in Example A6 and 10 g of gelatin were dispersed in 100 g of water to obtain a matting agent-containing composition. This matting agent-containing composition was coated on the emulsion layer to obtain a test film. The amount of matting agent used is 0.025 g / m.²Met.
[0071]
  When the test film was developed by a conventional method after exposure to the test pattern, a good image was obtained. Further, antiblocking properties and matting agent retention properties were evaluated by the following methods.
(Anti-blocking property)
  Five test films before development are stacked and allowed to stand at 25 ° C. for 1 week.ThisThe degree of peeling of each test film was examined. The test film was judged as ○ when the film was peeled off, △ when it was a little difficult to peel off, and x when it was hard to peel off.
(Matting agent retention properties)
  The test film before development was cut into a width of 5 cm and a length of 30 cm and wound around a stainless steel shaft having a diameter of 1 cm, and then the shaft was rolled at a speed of 1 cm / sec to peel off the film. After repeating this operation 10 times, the amount of the matting agent on the film was examined with an optical microscope. A case where almost no matting agent remained was judged as ◯, conversely, a case where almost no matting agent remained was judged as ×, and an intermediate product was judged as Δ.
[0072]
The antiblocking property and matting agent retention property of the test film of Example C1 were both good.
(Comparative Example C1)
Instead of the composite silica fine particles (Z-6) obtained in Example A6, a spherical silica fine particle powder “Seahoster KE-P100” manufactured by Nippon Shokubai Co., Ltd. was used in the same manner as in Example C1, A comparative test film was obtained. When the test film was developed by a conventional method after exposure of the test pattern, a good image was obtained. Further, the anti-blocking property was ○, but the matting agent retention property was Δ.
[0073]
【The invention's effect】
The composite silica fine particle of the present invention is a composite silica fine particle having excellent affinity for the matrix resin and having no variation in physical properties. The method for producing the composite silica fine particle of the present invention makes it easy to use the composite silica fine particle. Can be manufactured.
The composite silica fine particle dispersion of the present invention can be handled in a dispersed state without aggregating the composite silica fine particles, and is excellent in handleability.
[0074]
The plastic film of the present invention does not drop off the composite silica fine particles, has sufficient slipperiness, and is excellent in wear resistance. Therefore, the plastic film can be used for a magnetic tape, an optical photographic film, a condenser film, a thermal transfer printing film, a packaging film, etc. Among them, the magnetic film plastic film can realize excellent magnetic properties and runnability. .
[0075]
The matting agent of the present invention can impart excellent antiblocking properties and does not easily fall off. Further, when this matting agent is used for a silver halide light-sensitive material, image characteristics, stability and the like can be imparted.

Claims (10)

A method of obtaining composite silica fine particles by compositing spherical silica fine particles having an alkoxy group on the surface with an organic polymer,
This compounding process
In a dispersion in which the spherical silica fine particles are dispersed,
An organic chain and at least one polysiloxane group per molecule, and at least one Si-OR ¹ group (R ¹ is selected from a hydrogen atom, an alkyl group, and an acyl group in the polysiloxane group) and at least one group, the alkyl and acyl groups a group which may be substituted; when R ¹ are a plurality in one molecule contains a plurality of R ¹ may be different from each other). By hydrolyzing and condensing the organic polymer (P),
A step of compounding the spherical silica fine particles,
A method for producing composite silica fine particles, wherein The method for producing composite silica fine particles according to claim 1, wherein the spherical silica fine particles are obtained by an alkoxide method. The composite silica fine particle production according to claim 1 or 2, wherein the dispersion contains an organic solvent, and the organic solvent essentially comprises at least one selected from alcohols, ketones and ethers. Method. The method for producing composite silica fine particles according to any one of claims 1 to 3, wherein a catalyst is used in the hydrolysis / condensation, and the catalyst is a basic catalyst. The manufacturing method of the composite silica fine particle in any one of Claim 1 to 4 which performs the said hydrolysis and condensation at the temperature of 0-70 degreeC. The method for producing composite silica fine particles according to any one of claims 1 to 5, wherein tetraalkoxysilane is mixed with an organic solvent, water and a catalyst, and the mixture is mixed with an organic polymer (P). Composite silica fine particles obtained by the production method according to any one of claims 1 to 6 . A composite silica fine particle dispersion in which the composite silica fine particles according to claim 7 are dispersed in a dispersion. A plastic film in which the composite silica fine particles according to claim 7 are dispersed in a matrix resin. A matting agent comprising the composite silica fine particles according to claim 7 .